Article
Polymer Science
Naoki Shida, Kazuyuki Ninomiya, Natsuki Takigawa, Keiichi Imato, Yousuke Ooyama, Ikuyoshi Tomita, Shinsuke Inagi
Summary: A postpolymerization nucleophilic aromatic substitution reaction is used to efficiently diversify conjugated polymers, with complete substitution achieved by thiophenol derivatives and carbazole, while disubstitution occurs with para-selectivity by phenol derivatives.
Article
Chemistry, Multidisciplinary
Lucie Finck, Martin Oestreich
Summary: This study presents a chemoselective C(sp(2))-C(sp(2)) coupling of electron-deficient fluorinated arenes and functionalized N-aryl-N'-silyldiazenes as masked aryl nucleophiles. The fluoride-promoted transformation involves in situ generation of aryl nucleophiles with sensitive functional groups followed by a stepwise SNAr reaction. These reactions proceed rapidly at room temperature, allowing for functionalization of both coupling partners and yielding highly fluorinated biaryls in good yields.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Shobhan Mondal, Ester Maria Di Tommaso, Berit Olofsson
Summary: Efficient protocols for accessing iodo-substituted diaryl and aryl(vinyl) sulfides have been developed using iodonium salts as reactive electrophilic arylation and vinylation reagents. The reactions take place under transition-metal-free conditions, employing odorless and convenient sulfur reagents. A wide variety of functional groups are tolerated in the S-diarylation, enabling the regioselective late-stage application of several heterocycles and drug molecules under mild reaction conditions. A novel S-difunctionalization pathway was discovered using vinyliodonium salts, which proceeds under additive-free reaction conditions and grants excellent stereoselectivity in the synthesis of aryl(vinyl) sulfides. A one-pot strategy combining transition-metal-free diarylation and subsequent reduction provided facile access to electron-rich thioanilines and a direct synthesis of a potential drug candidate derivative. The retained iodo group allows a wide array of further synthetic transformations. Mechanistic insights were elucidated by isolating the key intermediate, and the relevant energy profile was substantiated by DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Dace Cirule, Irina Novosjolova, Erika Bizdena, Maris Turks
Summary: A new approach was developed for the synthesis of C6-substituted 2-triazolylpurine derivatives, resulting in a series of products with up to 87% yields obtained through SNAr reactions. The study demonstrates the ability of the 1,2,3-triazolyl ring at the C6 position of purine to act as an effective leaving group.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Biochemistry & Molecular Biology
Michal Barbasiewicz, Michal Fedorynski, Rafal Loska, Mieczyslaw Makosza
Summary: The aim of this essay is to reveal the similarity in a wide range of reactions between nucleophiles and p-electrophiles, regardless of whether they are aromatic or aliphatic. These reactions involve reversible addition followed by various transformations, common for both aliphatic and aromatic electrophile adducts. The understanding of this analogy is expected to broaden the scope of known reactions and inspire the exploration of new reactions that have been overlooked.
Article
Chemistry, Applied
Fabienne Hoffmann-Emery, Katrin Niedermann, Pankaj D. Rege, Manuel Konrath, Christian Lautz, Anne Katrin Kraft, Carine Steiner, Fritz Bliss, Andre Hell, Rolf Fischer, Diane E. Carrera, Danial Beaudry, Remy Angelaud, Sushant Malhotra, Francis Gosselin
Summary: A sustainable second-generation process for GDC-0134 was developed to meet the safety and greenness requirements of supplying pivotal clinical studies. The process involved the discovery of alternative solvents and improved reaction conditions, resulting in a significant reduction in process mass intensity and the successful production of a large amount of GDC-0134.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
Article
Chemistry, Multidisciplinary
Shinichiro Fuse, Sena Kanda, Hisashi Masui
Summary: Valuable indole derivatives were synthesized via the sequential 1,2-addition/nucleophilic substitution of indolyl-3-carbaldehydes. Microflow technology was used to suppress undesired reactions caused by unstable intermediates, leading to higher yields and reproducibility. The study provides a rapid and efficient method for the synthesis of structurally diverse indole derivatives.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Review
Chemistry, Applied
Alessandro Palmieri, Marino Petrini
Summary: The limited nucleophilic character and bidentate nature of unactivated nitroalkane anions make alkylation and allylation procedures troublesome. This review summarizes the most rewarding approaches, mainly based on metal-catalyzed processes involving purely ionic or mixed ionic-radical intermediates, that have been devised to overcome this limitation.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Inorganic & Nuclear
Naoki Matsushita, Myuto Kashihara, Michele Formica, Yoshiaki Nakao
Summary: Through the use of a new designed ligand, Pd-catalyzed etherification of nitroarenes with arenols was achieved, allowing for the direct access to a range of unsymmetrical diaryl ethers. The design of the ligand facilitated both the oxidative addition and reductive elimination steps of the catalytic cycle, providing mechanistic insights for optimizing the reaction.
Correction
Chemistry, Multidisciplinary
Kun-Xu Teng, Li-Ya Niu, Yan-Fei Kang, Qing-Zheng Yang
Summary: This study discusses a rational design of a dual lock-and-key supramolecular photosensitizer based on aromatic nucleophilic substitution for specific and enhanced photodynamic therapy.
Article
Chemistry, Multidisciplinary
Eduardo Rodrigo, Rainer Wiechert, Magnus W. Walter, Wilfried Braje, Herve Geneste
Summary: By using KOH, the direct F to OH exchange of aromatic and heteroaromatic substrates can be achieved under mechanochemical conditions, making the process more atom economical and environmentally friendly compared to other methods.
Article
Multidisciplinary Sciences
Ankit Thakuri, Mainak Banerjee, Amrita Chatterjee
Summary: In this study, a rapid and convenient method for the synthesis of unsymmetrical azo dyes was developed using microwave-assisted and metal-catalyst-free techniques. The effects of electronic and substituent groups on the reaction were thoroughly understood through competitive reactions.
Review
Chemistry, Organic
Harry C. Sample, Mathias O. Senge
Summary: The study details the SNAr reactions of seven types of porphyrinoids with different pyrrole units, analyzing the substitution dependent on the type of nucleophile and the site of substitution. Nucleophilic substitution on porphyrinoids is found to be an cost-effective procedure with the ability to yield complex substituent patterns, regardless of the type of porphyrinoid.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Laura Santos, Florian Audet, Morgan Donnard, Armen Panossian, Jean-Pierre Vors, David Bernier, Sergii Pazenok, Frederic R. Leroux
Summary: An efficient method for the synthesis of high-value N-polyfluoroalkyl anilines, primary polyfluoroalkylamines, and N,N-bis(polyfluoroalkyl) amines via N-polyfluoroalkylation of sulfonamides and phthalimide derivatives using sulfuryl fluoride (SO2F2) is reported. The in situ formation of polyfluoroalkyl fluorosulfonates from commercially available fluorinated alcohols and economical sulfuryl fluoride is advantageous in terms of environmental impact and cost. This general method allows for the polyfluoroalkylation of a variety of substrates, providing valuable building blocks for life science applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Mieczyslaw Makosza
Summary: Analysis of the effects of various parameters on reactions of C, N, and O nucleophiles with nitroarenes reveals two major pathways: direct addition leading to substitution of hydrogen or halogens, and single electron transfer (SET) leading to other processes. In some rare cases, paramagnetic species generated by SET can combine, resulting in substitution.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
